Butene polycarboxylic acid esters

ABSTRACT

NOVEL COMPOUNDS HAVING THE FOLLOWING FORMULA:   CH2=C(-CO-R1)-CH(-COO-R&#39;&#39;)-CH2-COO-R&#34;   WHEREIN R&#39;&#39; AND R&#34; ARE THE SAME OR DIFFERENT AND REPRESENT AN ALKYL GROUP HAVING UP TO 18 CARBON ATOMS, AN ALKENYL GROUP HAVING UP TO 18 CARBON ATOMS, AN ARYL GROUP HAVING UP TO 10 CARBON ATOMS, AN ARALKYL GROUP HAVING UP TO 10 CARBON ATOMS, OR A CYCLOALKYL GROUP HAVING UP TO 10 CARBON ATOMS; WHEREIN R1 REPRESENTS HYDROGEN, AN ALKYL GROUP HAVING UP TO 6 CARBON ATOMS, AN ARYL GROUP HAVING UP TO 10 CARBON ATOMS OR   -N(-R2)-R3   WHEREIN R2 AND R3 ARE THE SAME OR DIFFERENT AND EACH REPRESENTS AN ALKYL GROUP HAVING UP TO 6 CARBON ATMS OR A PHENYL GROUP OR WHEN TAKEN TOGETHER R2 AND R2 REPRESENT AN ALKYLENE OR OXYALKYLENE GROUP HAVING 4 OR 5 CARBON ATOMS.

United States Patent US. Cl. 260-475 SC 7 Claims ABSTRACT OF THEDISCLOSURE Novel compounds having the following formula:

CH2=C-COR1 CH-COOR' CHPCOOR" wherein R and R are the same or differentand each represents an alkyl group having up to 6 carbon atoms or aphenyl group or when taken together R and R represent an alkylene oroxyalkylene group having 4 or 5 carbon atoms.

This is a division of our co-pending application Ser. No. 627,289, filedMar. 31, 1967, now Pat. No. 3,538,- 147.

This invention relates to novel 3-butene-1,2-dicarboxylic acid esters.More particularly this invention relates to3-butene-3-carbamoyl-1,2-dicarboxylic acid esters and3-butene-3-carbonyl-l,Z-dicarboxylic acid esters.

It has been found that novel butene polycarboxylic acid esters can bemanufactured by reacting an acrylic compound selected from the groupconsisting of acrolein, vinyl ketones and N,N-disubstituted acrylicamides with an ethylene dicarboxylic acid ester selected from the groupconsisting of maleic acid esters and fumaric acid esters in the presenceof an organic tertiary phosphorus (III) compound selected from the groupconsisting of tertiary phosphines and tertiary phosphoamides.

The novel compounds of this invention have the following formula:

CH2O O O R (I) wherein R and R are the same or different and representan alkyl group having up to 18 carbon atoms, an alkenyl group having upto 18 carbon atoms, an aryl group having up to carbon atoms, an aralkylgroup having up to 10 carbon atoms; or a cycloalkyl group having "ice upto 10 carbon atoms; wherein R represents hydrogen, an alkyl group havingup to 6 carbon atoms, e.g., methyl, ethyl, propyl, isopropyl, butyl,n-pentyl, and n-hexyl and preferably methyl, an aryl group having up to10 carbon atoms, e.g., phenyl and naphthyl, or

wherein R and R are the same or different and each represents an alkylgroup having up to 6 carbon atoms or a phenyl group or when takentogether R and R represent an alkylene or oxyalkylene group having 4 or5 carbon atoms.

It is a principal object of the invention to provide novel3-butene-1,2-dicarboxylic acid esters.

It is a further object of this invention to provide novel3-butene-3-carbamoyl-1,2-dicarboXylic acid esters.

It is a still further object of this invention to provide novel3-butene-3-carbonyl-1,2-dicarboxylic acid esters.

It is a still further object of this invention to provide compoundswhich are useful as starting materials in polymerization reactions.

Other objects and advantages of the novel compounds of this inventionwill become more apparent from the following more detailed descriptionthereof.

Specific examples of the novel 3-butene-3-carbonyl-1,2 dicarboxylic acidesters of this invention include the following compounds:

1,Z-dimethoxycarbonyl-S-acetyl butene-3, 1,2-diethoXycarbonyl-3-acetylbutene-3, 1,Z-dimethoxycarbonyl-3-formyl butene-3,1,2-diethoxycarbonyl-3-tormyl butene-3, 1,Z-diallyloxycarbonyl-3-formylbutane-3, 1,2-dimethoXycarbonyl-3-benzoyl butene-3,1,2-diallyloxycarbonyl-3-benzoy1 butene-3,1,Z-dicyclohexyloxycarbonyl-3-benzoyl butene-S, etc.

The novel 3-butene-B-carbamoyldicarboxylic acid esters of this inventioninclude the following compounds:

1,2-dimethoxycarbonyl-3-dimethylcarbamoyl butene-3,1,Z-diethoxycarbonyl-3-diethylcarbamoyl butene-3,1,2-dimethoxycarbonyl-3-dimethylcarbamoy1 butene-3,1,2-di-n-butoxycarbonyl-3-di-n-butylcarbamoyl butene-3,1,2-diethoxycarbonyl-3- (N-methyl-N-n-butyl) carbamoyl butene-3,1,2-dimethoXycarbonyl-3-(N-methyl-N-n-butyl) carbamoyl butene-3,1,2-diethoxycarbonyl-3-(N-methyl-N-phenyl) carbamoyl butene-3,1,2-dimethoxycarbonyl-3-(N-methyl-N-phenyl) carbamoyl butene-3,1,Z-dimethoxycarbonyl-B-morpholinocarbonyl butene-3,1,2-diethoxycarbonyl-3-morpholinocarbonyl butene-3,1,2-dimethoxycarbonyl-3-piperidinocarbonyl butene-3,l,2-diethoxycarbonyl-3-piperidinocarbonyl butene-3,1,2-dicyclohexylcarbonyl-3-piperidinocarbonyl butene-3,1,Z-dicyclohexyloxycarbonyl-3-piperidinocarbonyl butene-3,

l,2-diallyloxycarbonyl-B-dimethylcarbamoyl butene-3 andl,2-diphenoxycarbonyl-3-diethylcarbamoyl butene-3, etc.

Of the above compounds, 1,2-dimethoxycarbonyl-3- formyl-butene-3,1,2-diethoxycarbonyl-3-formyl-butene- 3, l,Z-dimethoxycarbonyl-3-acetylbutene-3 and 1,2-diethoxycarbonyl-3-acetyl butene-3 are preferred.

The novel 3-butene-1,2-dicarboxylic acid esters of the present inventioncan be utilized as starting materials for the production of polymers. Inparticular, by copolymerizing the compounds of this invention with amonomer, such as styrene, acrylonitrile, acrylic acid, acrylic esters,methacrylic acid, methacrylic esters and vinyl acetate, the impactstrength and adhesive property of the resultant copolymer is improved.When the compounds of this invention are converted to their acidanhydrides, they are useful as curing agents for epoxy resins and thelike. The tendency for easy decarbonization of these compounds alsomakes them useful as blowing agents.

The novel 3-butene-1,2-dicarboxylic acid esters of this invention can beproduced by reacting an acrylic compound of the formula:

CH CHCOR (II) (wherein R has the meaning as already defined above) witha maleic acid ester of the formula:

CH-COOR (wherein R and R have the meaning as already defined above) or afumaric acid ester of the formula:

OHCOOR TWO C-HC (111') (wherein R and R" have the meaning as alreadydefined above) in the presence of a catalytic amount of an organictertiary phosphorus (III) compound selected from the group consisting oftertiary phosphines and tertiary phosphoamide.

Examples of starting acrylic compounds of Formula II, which are known inchemical literatures, are as follows:

Acrolein; vinyl alkyl ketones such as vinyl methyl, vinyl ethyl, vinylpropyl, vinyl butyl, vinyl pentyl and vinyl hexyl ketone; and vinyl arylketones such as vinyl phenyl, vinyl tolyl, vinyl p-methoxy phenyl, vinylp-chlorophenyl and vinyl naphthyl ketone; and N,N-di-substitutedacrylamide such as the following N-n-dialkyl substituted acrylamidecompounds: N,N-dimethyl, N,N-diethyl, N,N-dipropyl, N-methyl-N-ethyl,N,N-dibutyl, N,N-dipentyl and N,N-dihexyl acrylamide, N,N-diarylsubstituted acrylamide such as N,N-diphenyl, N,N-ditolyl,N,N-di-(pmethoxy phenyl), N,N-di-(p-chloro-phenyl), N-methyl-N- phenyl,acryloyl morpholine and acryloyl piperidine, etc.

The maleic acid esters and fumaric acid esters to be reacted with theacrylic compound of the Formula II include the following:

The dialkyl maleates or fumarates such as dimethyl, diethyl, dipropyl,dibutyl, dipentyl, diheptyl, dioctyl, dinonyl, didecyl, didodecyl,diheptadecyl, dioctadecyl, methyl ethyl, methyl butyl, and ethyl butylmaleate or fumarate; the dialkyl maleates or fumarates such as divinyl,diallyl, diisopropenyl maleates or fumarates; diaryl maleates orfumarates such as diphenyl, ditolyl, di(p-methoxyphenyl),di-(p-chlorophenyl), phenyl-tolyl, and phenyl-p-chlorophenyl maleates orfumarates; the diaralkyl maleates or fumarates such as dibenzyl,diphenylethyl, and benzyl phenylethyl maleates or fumarates; thedicycloalkyl maleates or fumarates such as dicyclopentyl, dicyclohexyland cyclopentyl-cyclohexyl maleates or fumarates, etc.

4 The organic tertiary phosphorus (III) compound used as the catalyst isselected from the group consisting of tertiary phosphines and tertiaryphosphoamides which have the following formula:

wherein R R and R are the same or different and represent an alkyl grouphaving up to 8 carbon atoms which alkyl group may have a cyano,carbonyl, hydroxy, hydroxycarbonyl or alkoxycarbonyl group having up to9 carbon atoms substituted thereon, a cycloalkyl group having 5 to 8carbon atoms, an aryl, preferably phenyl; any two of R R and R may forma hetero ring together with the phosphorus atom,

wherein R and R are the same or different and represent an alkyl grouphaving up to 8 carbon atoms, a cycloalkyl group having 5 or 6 carbonatoms, an aryl group, preferably a phenyl group, or R or R togetherrepresent an alkylene or oxyalkylene having 4 or 5 carbon atoms orwherein R and R are the same or different and represent an alkyl grouppreferably having up to 8 carbon atoms, a cycloalkyl having 5 or 6carbon atoms or any aryl group, preferably a phenyl group.

Examples of the tertiary phosphines useful as catalysts for producingthe novel compounds of this invention are: trialkyl phosphines such astrimethyl, triethyl, tripropyl, triisobutyl, tributyl, trihexyl andtrioctylphosphine; tricycloalkyl phosphines such as tricyclopentyl,tricyclohexyl, and cyclopentyl dicyclohexyl phosphine; triarylphosphinessuch as triphenyl phosphine; alkyl diaryl or dialkyl aryl phosphinessuch as isobutyl diphenyl diisobutyl phenyl, 4-hydroxy butyl diphenyland phenyl diethylphosphine; alkyl dicycloalkyl or dialkyl cycloalkylphosphines such as ethyl dicyclohexyl, diethyl cyclohexyl, butyldicyclohexyl dibutyl cyclohexyl, dicyclohexyl-Z-cyanoethyl,cyclohexyI-di-(Z-cyanoethyl), dicyclohexyl 2 methoxycarbonylethyl,cyclohexyl-di-(Z-hydroxycarbonyl) and dicyclohexyI-Z-butyroyl phosphine;and tertiary phosphines such as compounds having the following formulae:

Examples of the teritary phosphoamides are tris (dialkylamino)phosphines such as tris (dimethylamino), tris (diethylamino), tris(diisopropylamino) tris (dibutylamino) and tris (diisobutylamino)phosphine, tris (dicycloalkylamino) phosphines such as tris(dicyclopentylamino), tris (dicyclohexylamino) phosphine and the like,tris (diarylamino) phosphines such as tris (diphenylamino) atris(ditolyl amino) and tris (di-p-chlorophenylamino) phosphine,tertiary phosphoamides wherein R and R together form an alkylene oroxyalkylene group having 4 or 5 carbon atoms such as trimorpholino,tripiperidino and tripyrrolidino phosphine, tertiary phosphoamideshaving different substituents such as tris (N-methyl-N-phenylamino) tris(N-methyl-N-ethylamino), tris (N-ethyl-N-cyclohexylamino), tris(N-phenyl-N-cyclohexylarnino), methyl dimorpholino, ethyl dimorpholino,cyclo hexyl dipyrrolidino, phenyl dipyrrolidino and diphenyl morpholinophosphine; and tertiary phosphines wherein R R and R are such astetracyclohexyl diphosphine, tetradiisobutyl phosphine, tetradibutylphosphine and butyl tricyclohexyl phosphine.

Also suitable as catalysts in the process of the invention are catalystswherein the teritary phosphine moiety is contained within a metalcomplex, such as a modified metal carbonyl complex of a transitionmetal.

Especially preferably among the above-mentioned or ganic tertiaryphosphorus (III) compounds are tertiary phosphines wherein a secondarycarbon atom is linked with a phosphorus atom, such as teriary phosphinehaving a cycloalkyl group such as tricyclopentyl phosphine,tricyclohexyl phosphine, tricycloheptyl phosphine, tris(methylcyclohexyl) phosphine, tricycloctyl phosphine, trinorbornylphosphine, butyl dicyclohexyl phosphine, ethyl di-cyclohexyl phosphine,diethyl cyclohexyl phosphine and dibutyl cyclohexyl phosphine andtertiary phosphoamides wherein R and R have 3 to 8 carbon atoms such astris (dialkyl amino) phosphine such as tris (di-nbutylamino) phosphineand tris (di-isobutylamino) phosphine.

In this invention, the amount of ethylene dicarboxylic acid ester can bedetermined according to the amount used in an ordinary stoichiometricalreaction, and is in general 0.1 to 5 mole equivalents, preferably 0.3 to1.5 mole equivalents, based on the acrylic compound.

The reaction of this invention proceeds in the presence of the organictertiary phosphorus (III) compound in a catalytic amount or in an amountof 0.0001 to 0.1 mole equivalent based on the acrylic compound but doesnot proceed in its absence. The amount can be increased optionally.

The reaction temperature is ordinarily 0 to 200 C., and preferably 30 to120 C.

A polymerization inhibitor such as tert.-butylpyrocatechol andpyrohydroquinone may also be added to the reaction system.

It is also preferable that the atmosphere of the reaction system shouldbe non-oxidizing.

The use of an inert solvent is not necessary, but the following solventscan be used with good results: Ethers such as dimethyl and diethylether, dioxane, tetrahydrofuran, alcohols such as ethyl, isopropyl,tert.-butyl alcohol, sec.-butyl, sec.-amyl, tert.-amyl, octyl and decylalcohol, aromatic hydrocarbons such as benzene, toluene and xylene, andcompounds with a nitrogen-containing organic base such as dimethylformamide, pyridine, triethyl amine and trimethyl amine.

When the reaction of this invention has sufiiciently proceeded, theorganic tertiary phosphorus (III) compound may be inactivated byaddition to the reaction system of a catalyst-inactivating agent such asadipic acid and p-toluenesulfonic acid.

The method of this invention also includes an embodiment wherein3-butene-3-N-substituted carbamoyl- 1,2-dicarboxylic acid ester can beconverted into 3-butene- 1,2,3-tricarboxylic acid by heating in an acidor alkali aqueous solution for hydrolysis.

3-butene-polycarboxylic acid ester can be converted to3-butene-polycarboxylic acid ester having other ester group by heatingin an alcohol in the presence of an ester-interchange catalyst such assulfuric acid. 3-butene tricarboxylic acid or its esters can beconverted into 3- butene polycarboxylic acid or its esters by reductionwith hydrogen gas in the presence of a reducing catalyst such as nickeland palladium. These 3-butuenetricarboxylic acids or their esters findwide applications as plasticizers, enamels for electric wires andwater-soluble paints. If 3-butene-1,2,3-tricarboxylic acid is heated toabout 200 C., it can be converted to dimethylmaleic anhydride.

The following examples illustrate the preferred embodiments of the novelcompounds of this invention only and should not be taken as limiting.

EXAMPLE 1 A solution of 3.0 g. of acrolein, a polymerization inhibitorand 150 g. of dioxane was addedv dropwise to a well-stirred solution of15 g. of diethyl fumarate and 0.6 g. of tricyclohexyl phosphine in anatmosphere of nitrogen at room temperature. After the reaction mixturewas stirred for 9 hours, a small amount of adipic acid was added to stopthe reaction The mixture was distilled to remove the solvent and 2.5 g.of 1,2-diethoxycarbonyl- 3-formyl butene-3 were isolated byrectification.

EXAMPLE 2 A solution of 6 g. of methyl vinyl ketone, a polymerizationinhibitor and 50 g. of dioXane Was added dropwise to a well-stirredsolution of 10 g. of diethyl fumarate and 0.7 g. of tricyclohexylphosphine in an atmosphere of nitrogen at room temperature. After thereaction mixture was stirred continuously overnight, the reaction wasstopped by adding a small amount of adipic acid. The dioxane wasdistilled ofi and 11.5 g. of 1,2-diethoxycarbonyl-3-acetyl butene-3 wasisolated by rectification.

EXAMPLE 3 A solution of 5.2 g. of methyl vinyl ketone, a polymerizationand g. of dioxane was added dropwise to a well-stirred solution of 19 g.of dimethyl fumarate and 0.6 g. of tricyclohexyl phosphine in a nitrogenatmosphere at room temperature. After stirring the reaction mixture for10 hours, a small amount of adipic acid was added to stop the reaction.The dioxane was distilled off and 13.8 g. of 1,2-dimethoxycarbonyl-3acetyl butene-3 was isolated by rectification.

EXAMPLES 4-14 A solution of a vinyl ketone derivative containing apolymerization inhibitor was added dropwise with good stirring to asolution containing either a fumaric acid ester of a maleic acid esterand a catalyst in an atmosphere of nitrogen at a predeterminedtemperature. The reaction mixture was stirred for a predetermined lengthof time and a small amount of adipic acid was added to the reactionmixture. The solvent was removed by distillation and the reactionproduct was isolated by rectification. Results are shown in Table I inwhich Me=methyl, Et=ethyl and ph=phenyl.

9 What is claimed is: 1. A 3-butene-1,2-dicarboxylic acid ester of theformula:

wherein R and R" are the same or diiferent and are selected from thegroup consisting of an alkyl group having up to 18 carbon atoms, andhydrocarbon aralkyl group having up to 10 carbon atoms, and a cycloalkylgroup having 5 0r 6 carbon atoms; wherein R is selected from the groupconsisting of hydrogen, an alkyl group having up to 6 carbon atoms, anda hydrocarbon aryl group having up to 10 carbon atoms.

2. A butene polycarboxylic acid ester according to claim 1 wherein saidester is 1,2-dimethoxycarbonyl-3- acetyl butene-3.

3. A butene polycarboxylic acid ester according to claim 1 wherein saidester is 1,2-diethoxy carbonyl-3- acetyl butene-3.

4. A butene polycarboxylic acid ester according to claim 1 wherein saidester is 1,2-dimethoxycarbonyl-3- formyl butene-3.

References Cited UNITED STATES PATENTS 2,594,488 4/1952 Patrick 260-4832,798,793 9/1964 Moore 260483 3,155,685 11/1964 Prill et a1. 260-4833,151,128 9/1964 Lardelli et a1. 260-483 JAMES A. PATTEN, PrimaryExaminer V. GARNER, Assistant Examiner US. Cl. X.R.

260--31.8 J, 31.8 R, 63 UY, 67 A, 67 DA, 73 R, 247.2 B, 294.3 B, 346.8,471 R, 479 S, 482 P, 483, 537 S

